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WO2011028249A1 - Grains colorés - Google Patents

Grains colorés Download PDF

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Publication number
WO2011028249A1
WO2011028249A1 PCT/US2010/002323 US2010002323W WO2011028249A1 WO 2011028249 A1 WO2011028249 A1 WO 2011028249A1 US 2010002323 W US2010002323 W US 2010002323W WO 2011028249 A1 WO2011028249 A1 WO 2011028249A1
Authority
WO
WIPO (PCT)
Prior art keywords
colored
releasing agent
coloring agent
colored speckle
carrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2010/002323
Other languages
English (en)
Inventor
Gregory Fernandes
Eduardo Torres
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Milliken and Co
Original Assignee
Milliken and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Milliken and Co filed Critical Milliken and Co
Priority to EP10749928A priority Critical patent/EP2470631A1/fr
Priority to CN2010800377084A priority patent/CN102482618A/zh
Priority to IN367DEN2012 priority patent/IN2012DN00367A/en
Priority to JP2012526720A priority patent/JP2013503237A/ja
Publication of WO2011028249A1 publication Critical patent/WO2011028249A1/fr
Priority to ZA2012/00941A priority patent/ZA201200941B/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/221—Mono, di- or trisaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents

Definitions

  • This invention relates to non-bleeding and quick color releasing colored speckles for use in granular laundry detergents and other consumer products.
  • the speckles are comprised of a porous carrier, a releasing agent, and a coloring agent.
  • WO 2006/099964 A1 to Andrade et al. discloses the use of a speckle granule comprised of a clay mineral carrier and a mica pigment.
  • a speckle granule comprised of a clay mineral carrier and a mica pigment.
  • this reference teaches the inclusion of a soluble builder salt, such as sodium tripolyphosphate, admixed with the clay in the granule.
  • a water- soluble polymeric coating, such as polyvinyl alcohol, may also be added to the granule, to help prevent the mica from leaving the clay during storage and handling.
  • the problems associated with previous attempts by others to include colored speckles in detergents include fabric staining from the colorant used in the speckles, bleeding and transferring of the colorant to the surrounding detergent powder, and failure of the speckle to release the colorant rapidly into the wash water.
  • the present disclosure addresses and overcomes these problems.
  • the colored speckles of the present disclosure are ideally suited for providing color to various other compositions including, but not limited to granular detergent compositions (such as laundry detergent compositions).
  • the colored speckles may provide non-staining, aesthetically- pleasing features to textile substrates treated therewith. They also resist bleeding or 5 transferring to the surrounding detergent composition.
  • the colored speckles of the present disclosure quickly release color from the porous carrier and provide desirable color to the wash water. For these reasons, and others that will be described herein, the present colored speckles represent a useful advance over the prior art. i o Brief Summary of the Invention
  • a colored speckle comprising a majority by weight of at least one porous carrier material; at least one releasing agent selected from the group consisting of salt compounds, sugar compounds, alkoxylated aromatic compounds, glycols, high molecular weight alcohols, solvents having a boiling point above 60°C, and mixtures thereof; and at least 15 one coloring agent.
  • Yet another alternative includes a colored speckle comprising a majority by weight of at least one porous carrier material selected from clays, silicas, zeolites, metal oxides, diatomaceous earth, mica, talc, chalk, gypsum-containing compounds, leaded zinc oxide, zinc oxide, zinc
  • 25 releasing agent selected from the group consisting of salt compounds, sugar compounds, alkoxylated aromatic compounds, glycols, high molecular weight alcohols, solvents having a boiling point above 60°C, and mixtures thereof; and at least one polymeric coloring agent.
  • a colored speckle comprising at least one porous carrier material, wherein the at least one porous carrier material is characterized by having a plurality of pores, a first layer comprising at least one releasing agent, wherein the releasing agent is in direct contact with at least a portion of the plurality of pores of the at least one porous carrier material, and a second layer comprising from about 0.01% to about 10% by weight of at least one coloring agent, wherein the colorant agent is in direct contact with at least a portion of the releasing agent layer.
  • a colored speckle comprising at least one porous carrier material, wherein the at least one porous carrier material is characterized by having a plurality of pores, and a mixture of at least one releasing agent and at least one coloring agent.
  • Another embodiment includes a method for forming a colored speckle comprising the steps of providing at least one porous carrier material; applying at least one releasing agent to the at least one porous carrier material to form a carrier-releasing agent composite; and applying at least one coloring agent to the carrier-releasing agent composite to form the colored speckle.
  • Yet another alternative is a method for forming a colored speckle comprising the steps of providing at least one porous carrier material; applying a mixture of at least one releasing agent and at least one coloring agent to the at least one porous carrier material to form the colored speckle.
  • the present disclosure relates to non-bleeding and quick color releasing colored speckles for use in granular detergent compositions.
  • the colored speckles are comprised of porous granules made from water-dispersible or water soluble materials which act as a carrier for a coloring agent and a releasing agent.
  • the porous carrier provides good resistance to color bleeding into the surrounding detergent composition.
  • the combined use of a releasing agent with the carrier allows for quick release (i.e. in less than 5 minutes) of the coloring agent from the carrier and into the wash water.
  • the present disclosure describes a colored speckle and a method for making the colored speckle which drastically improves the coloring agent release time, while still preserving the bleed resistance that the carrier provides.
  • non-staining generally refers to a coloring agent, or a composition that contains such a coloring agent, that may be washed or removed from substrate surfaces (e.g. skin, fabric, wood, concrete) with relatively little effort and without staining the substrate to an appreciable extent.
  • substrate surfaces e.g. skin, fabric, wood, concrete
  • non-bleeding generally refers to a coloring agent-containing composition that does not substantially color the material surrounding the composition under conditions wherein the material is not intended to be colored.
  • the colored speckles of the present invention will generally be considered to be “non-bleeding” if the colored speckles fail to substantially color the surrounding powdered detergent in its unused state (i.e. while it remains in the package).
  • a porous granule, or carrier has, by virtue of its form and/or structure, an abundance of pores both on its surface as well as in its interior that have a certain distribution of sizes, depths and tortuosity.
  • a coloring agent applied to porous granules would be drawn into these pores via capillary action, thereby being more "protected” or “shielded” from the external environment than if it were to rest only on the surface of the granule, which is believed to occur in a non-porous material contacted with a coloring agent.
  • the release rate of the coloring agent from such porous granules may then depend on the rate of disintegration, swelling or dispersion of the granule. These factors may result in a slower release of color from porous granules as compared to non-porous granules (again, where the coloring agent would be present only on the outer surface of the granule).
  • the interaction between the coloring agent and the material comprising the porous granule e.g. clay.
  • the coloring agent and the material comprising the porous granule e.g. clay.
  • the coloring agent and the granule, or carrier which may be provided by such by binding forces, adsorption, and the like, may further enhance the bleed resistance of the resulting colored speckle.
  • the interaction is too strong, it could inhibit the release rate of the coloring agent from the colored speckle into the wash water, even if the colored speckle granules disintegrates rapidly.
  • the coloring agent may be applied to the carrier in such a way that it is in contact (either absorbed or adsorbed) with a releasing agent, rather than with the carrier.
  • the releasing agent acts to prevent and/or reduce the coloring agent's interaction with the inner walls of the pores of the granule.
  • the coloring agent may be primarily in contact with the releasing agent, rather than with the surfaces of the carrier.
  • this structural arrangement of carrier to releasing agent to coloring agent may be achieved by adding a releasing agent to the inner walls or surfaces of the porous granule before application of the coloring agent. Forces such as capillary action may draw the coloring agent into the pores where the coloring agent is shielded from the external environment. This allows the coloring agent to be primarily in physical contact with the releasing agent and not in direct contact with the walls or surfaces of the porous granule, or carrier.
  • the amount of releasing agent required to deliver rapid release of the coloring agent from the porous granules may be directly dependent on the "porosity" of the granules, carriers, which includes factors like pore size distribution, depth and tortuosity of the pores, and the rate of disintegration of the granules. It is also believed that the strength of the interaction between the coloring agent and the carrier or carrier material may also have an effect on these desired features.
  • the carrier is preferably in the form of a porous granule which is characterized by having a plurality of pores.
  • the colored speckle may be comprised of a majority by weight of the carrier.
  • the material used to produce the porous granule may be characterized as a water dispersible material.
  • Suitable carrier materials that may be granulated to form these porous granules, or carriers may be selected from compounds containing and/or including, but not limited to clays, silicas, zeolites, metal oxides, diatomaceous earth, mica, talc, chalk, gypsum-containing compounds, leaded zinc oxide, zinc oxide, zinc sulfide, lithopone, titanium dioxide, calcium sulfate, antimony oxide, magnesium silicate, barytes, basic lead carbonate, calcium carbonate, calcium sulfate, barium sulfate, calcium silicate, silica flatting agents, aluminum silicate including hydrous aluminum silicates, magnesium silicates, calcium metasilicate, sodium-potassium- aluminum silicate, and the like, and combinations thereof.
  • Suitable examples of water soluble carriers include detergency builders such as sodium tripolyphosphate, sodium silicate, soda ash-containing compounds, and the like, and combinations thereof.
  • clay materials include bentonite, kaolin, smectite, illite, chlorite, hormite, beidelite, sepiolite, alunite, hydrotalcite, nontronite, hectorite, attapulgite, pimelite, muscovite, willemseite, minnesotaite, antigorite, amesite, china clay, halloysite, and the like, and combinations thereof.
  • suitable clay carriers include Pelben® 10 and Pelben® 35 (available from Buntech, a Brazilian company).
  • Suitable examples of clay powders include Argel® 10 and Argel® 40 (available from Buntech).
  • Bentonites are clays that are comprised primarily of, and whose properties are typically dictated by a smectite clay mineral (e.g. montmorillonite, hectorite, nontronite, etc.).
  • Smectites are generally comprised of stacks of negatively charged layers (wherein each layer is comprised of two tetrahedral sheets attached to one octahedral sheet; the tetrahedra formed by silicon and oxygen atoms and the octahedra formed by aluminum and oxygen atoms together with hydroxyl radicals) balanced and/or compensated by alkaline earth metal cations (e.g. Ca 2+ and/or Mg 2+ ) and/or alkali metal cations (eg.
  • alkaline earth metal cations e.g. Ca 2+ and/or Mg 2+
  • alkali metal cations e.
  • the relative amounts of the two types (alkaline earth metal and alkali metal) of cations typically determine the swelling characteristic of the clay material when placed in water.
  • Bentonites, in which the alkaline earth metal cation Ca 2+ is predominant (or is in a relative majority), are called calcium bentonites; whereas, bentonites in which the alkali metal cation Na + is predominant (or is in a relative majority) are called sodium bentonites.
  • natural refers to the presence of the mineral in deposits found in the earth (formed via modification of volcanic ash deposits in marine basins by geological processes). Accordingly, a natural deposit of bentonite containing primarily (or a relative majority of) Na + cations is referred to as "natural sodium bentonite;" whereas, a natural deposit of a bentonite predominantly containing (or containing a relative majority of) Ca 2+ cations is referred to as "natural calcium bentonite.
  • Synthetic analogues of Na and Ca bentonite may also be synthesized (by using hydrothermal techniques, for example).
  • Synthetic sodium bentonite may also refer to bentonite obtained by treatment of calcium bentonite with, but not limited to, sodium carbonate or sodium oxalate (to remove the calcium ion and substitute it with a sodium ion). This treatment can be varied to impart different levels of ion-exchange or Na + for Ca 2+ substitution.
  • these materials are referred to as “partially activated” and “fully activated” grades of clay material, respectively (with “fully” referring to maximum exchange of Ca 2+ for Na + ).
  • the material used to produce the porous granule may also be a water soluble material that does not have a rapid rate of dissolution (e.g. phosphates).
  • a rapid rate of dissolution e.g. phosphates.
  • rapid is intended to describe a dissolution rate that will allow the quick and/or instant release of the coloring agent into a wash water solution.
  • the carrier exhibits a particular range of particle size, as determined, for example, by sieving techniques according to ASTM D1921 - 06 ("Standard Test Method For Particle Size (Sieve Analysis) of Plastic Materials"). Alternative methods known to those skilled in the art may also be utilized for determining particle size. For example, other sieving techniques may be used or electronic laboratory equipment known for determining particle size may alternatively be employed.
  • ASTM D1921 - 06 Standard Test Method For Particle Size (Sieve Analysis) of Plastic Materials
  • Alternative methods known to those skilled in the art may also be utilized for determining particle size.
  • other sieving techniques may be used or electronic laboratory equipment known for determining particle size may alternatively be employed.
  • the carriers of the present invention it may be preferably that the carriers exhibit an average particle size of about 0.1mm to about 2mm, more preferably an average particle size of about 0.3mm to about 1.2mm. Coloring Agent
  • the coloring agent of the present invention is preferably a polymeric colorant.
  • polymeric colorant generally refers to a colorant having at least one chromophore portion attached to at least one oligomeric or polymeric chain, wherein the chain has at least three repeating units.
  • the oligomeric or polymeric constituent can be bound to the chromophore via any suitable means, such as a covalent bond, an ionic bond, or suitable electrostatic interaction.
  • the polymeric colorant may be characterized by having an absorbance in the range of between about 300 nanometers and about 900 nanometers, as measured by UV-vis spectroscopy.
  • the polymeric colorant has a molecular weight that is typically represented as a molecular weight distribution. Accordingly, the molecular weight of the polymeric colorant is generally reported as an average molecular weight, as determined by its molecular weight distribution.
  • the chromophore group of the colorant may vary widely, and may include compounds characterized in the art as dyestuffs or as pigments. The actual group used will depend to a large extent upon, for instance, the desired color and colorfastness characteristics.
  • the chromophore group may be attached to at least one polyalkyleneoxy-substituent through a suitable linking moiety of nitrogen, oxygen, sulfur, etc.
  • chromophore groups include nitroso, nitro, azo (including monoazo, disazo, trisazo, tetrakisazo, polyazo, formazan, azomethine and metal complexes thereof), stilbene, diarylmethane, triarylmethane, xanthene acridine, quinoline, methine (including polymethine), thiazole, indamine, indophenol, azine, thiazine, oxazine, aminoketone, hydroxyketone, anthraquinone (including anthrapyrazolines, anthrone, anthrapyridone, anthrapyrimidine, flavanthrone, pyranthrone, benzanthrone, perylene, perinone, naphthalimide and other structures formally related to anthraquinone), indigoid (including thioindigoid), phthalocyanine chromophore groups, and mixture
  • polyalkyleneoxy chains examples include polyalkyleneoxy chains.
  • polyalkyleneoxy generally refers to molecular structures containing the following repeating units: -CH 2 CH 2 0-, CH 2 CH 2 CH 2 0-, -CH 2 CH 2 CH 2 CH 2 0-, -CH 2 CH(CH 3 )0-, -CH 2 CH(CH 2 CH 3 )0- CH 2 CH 2 CH(CH 3 )0-, and any combinations thereof.
  • Typical of such groups which may be attached to the chromophore group are the polymeric epoxides, such as the polyalkylene oxides and copolymers thereof.
  • Typical polyalkylene oxides and copolymers of same which may be employed to provide the colorants include those made from alkylene oxide monomers containing from two to twenty carbon atoms, or more preferably, from two to six carbon atoms.
  • Examples include: polyethylene oxides; polypropylene oxides; polybutylene oxides; oxetanes; tetrahydrafurans; copolymers of polyethylene oxides, polypropylene oxides and polybutylene oxides; and other copolymers including block copolymers, in which a majority of the polymeric substituent is polyethylene oxide, polypropylene oxide and/or polybutylene oxide.
  • polyalkyleneoxy group may have an average molecular weight in the range of from about 132 to about 10,000, preferably from about 176 to about 5000.
  • the colorants may not ordinarily be chemically bound to the carrier, the precise chemical identity of the end group on the polyalkyleneoxy group may not be critical insofar as the proper functioning of the colorant is concerned in the composition.
  • certain most preferred colorants will be defined wherein certain end groups will be identified. Such recitation of end groups is not to be construed as limiting the invention in its broader embodiments in any way. According to such a most preferred embodiment the colorants may be characterized as follows:
  • R is an organic chromophore group
  • A is a linking moiety in said organic chromophore group selected from the group consisting of N, O, S or C0 2
  • the alkylene moiety of the alkyleneoxy constituent contains from 2 to about 4 carbon atoms
  • n is an integer of from 2 to about 230
  • m is 1 when A is O, S, C0 2 and 1 or 2 when A is N
  • x is an integer of from 1 to 5
  • the product of n times x times m (n.m.x) is from 2 to about 230, and is a member of the group consisting of
  • R 2 is H, an alkyl radical containing up to about 20 carbon atoms or carboxy-terminated alkyl radical containing up to about 20 carbon atoms
  • j and k are OH, OM or OR 3 wherein M is a cation moiety of an alkali metal, an alkaline earth metal, transition metal, e.g., nickel, etc. or ammonium
  • R 3 is an alkyl radical containing up to about 20 carbon atoms.
  • the oligomeric constituent can be any suitable constituent including, but not limited to, oligomeric constituents selected from the group consisting of (i) oligomers comprising at least three monomers, or repeating units, selected from the group consisting of C 2 -C 20 alkyleneoxy groups, glycidol groups, and glycidyl groups, (ii) aromatic or aliphatic oligomeric esters conforming to structure (I)
  • R 2 and R 3 are independently selected from the group consisting of hydrogen and C C 10 alkyl groups, f is an integer between and including 1 and 10, and g is any positive integer or fraction between and including 1 and 20.
  • suitable values for g include both integers and fractions because the length of the oligomeric constituent on the individual polymeric colorant molecules may vary.
  • the value for g represents an average length of the ester chain for a given sample or collection of polymeric colorant molecules.
  • the polymeric colorant can comprise one or more oligomeric constituents consisting of three or more ethylene oxide monomer groups.
  • Exemplary polymeric colorants include Liquitint® polymeric colorants, Cleartint® polymeric liquid concentrate colorants, Reactint® polymeric colorants, and Palmer® polymeric colorants, all of which are available from Milliken Chemical, a division of Milliken & Company of Spartanburg, SC.
  • Liquitint® polymeric colorants are characterized in that they are water soluble, non-staining, colorants. They are widely used in laundry detergents, fabric softeners, and other consumer and industrial cleaning products.
  • Liquitint® polymeric colorants are generally bright liquid colorants which exhibit excellent solubility in water, are compatible with other chemicals present in their end-use formulations, and are easy to handle.
  • Liquitint® polymeric colorants may be used to provide color in both aqueous and solid systems. The unique polymeric nature of Liquitint® polymeric colorants provides reduced staining to skin, textiles, hard surfaces, equipment, and the like.
  • Cleartint® polymeric liquid concentrate colorants are specially designed liquid colorants often used for coloring clarified polypropylene articles. These colorants may be incorporated into polypropylene resins easily without detrimentally affecting the clarity of the article to provide transparent, clear and brightly colored polypropylene articles.
  • Cleartint® liquid concentrate polymeric colorants are oligomeric coloring materials which combine the exceptional aesthetics of dyes with the migration resistance of pigments. These colorants may be used as light tints to mask residual haze, or they may be used for deep, rich shades that are not possible with pigment colorants.
  • Cleartint® liquid concentrate polymeric colorants allow clarified polypropylene to rival the beauty of higher cost plastic materials. The technical and physical property benefits of clarified polypropylene may be exploited without sacrificing product aesthetics.
  • Reactint® polymeric colorants are liquid polymeric colorants useful for coloring polyurethane and other thermoset resins. These colorants are reactive polymeric colorants that consist of chromophores which are chemically bound to polyols. This arrangement allows the polymeric colorant to react into the polyurethane polymer matrix. Unlike pigment pastes, which are dispersions of solid particles in a liquid carrier, Reactint® polymeric colorants are 100% homogeneous liquids that are soluble in polyol and will not settle over time. Because of this pure liquid and easy to disperse nature, it is possible to blend Reactint® colorants in-line and on-the-fly, while producing polyurethane foams and resins.
  • Palmer® polymer colorants are liquid colorants specially developed for use in washable applications, such as in markers, paints and other art products. They contain no heavy metals, are non-toxic, and have excellent non-staining properties on skin, fabric and other surfaces. Palmer® polymeric colorants have very good compatibility with aqueous ink formulations and provide bright colors.
  • a colorant selected from one or more of the following classes may be suitable for use as the coloring agent in the colored speckle: acid dyes, basic dyes, direct dyes, solvent dyes, vat dyes, mordant dyes, indigoid dyes, reactive dyes, disperse dyes, sulfur dyes, fluorescent dyes; pigments, both organic and inorganic; natural colorants; and the like.
  • the releasing agent is generally used to effectuate the quick release of the coloring agent from the carrier.
  • the releasing agent may be any material that is soluble or miscible in water at room temperature, though for ease of processing, it may be advantageous to use materials with moderate-to-high solubility in water (e.g. 20g-200g releasing agent/1 OOg water at 20°C). It may be advantageous if the releasing agent is a solid in its pure form at room temperature.
  • the solid releasing agent may be ionic in nature (e.g. salts such as magnesium sulfate, sodium sulfate, sodium carbonate, sodium chloride, and the like), non-ionic (e.g. sugars such as sucrose, fructose, and the like), or a mixture of ionic and non-ionic.
  • the releasing agent may also be a water-dispersible solid.
  • the coloring agent may exhibit a weaker binding affinity for the water dispersible releasing agent than for the carrier and/or the carrier material. Suitable examples of such releasing agents may be dependent upon and specific to the desired coloring agents utilized for the colored speckles.
  • the releasing agent may also be a soluble or miscible material that is not a solid at room temperature. Rather, the releasing agent may be a liquid or a wax in its pure form at room temperature.
  • Some examples of these types of releasing agents include alkoxylated aromatic compounds (such as alkoxylates of m-toluidine), glycols (such as polyethylene glycol), high molecular weight alcohols (such as ethanol, propanol, hexanol, and butanol), solvents having a boiling point above 60°C (such as dipropyl ether, ethylene glycol dimethyl ether, and toluene), and the like, and mixtures thereof.
  • alkoxylated aromatic compounds such as alkoxylates of m-toluidine
  • glycols such as polyethylene glycol
  • high molecular weight alcohols such as ethanol, propanol, hexanol, and butanol
  • solvents having a boiling point above 60°C such
  • the alkoxylated form of m-toluidine may be alkoxylated with one or more of the following groups: ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and any mixtures thereof.
  • EO ethylene oxide
  • PO propylene oxide
  • BO butylene oxide
  • the average number of groups forming the alkoxylated portion of m-toluidine may be from about 1 to about 200, more preferably from about 1 to about 100, and most preferably from about 1 to about 50.
  • a solid releasing agent may be "fixed” at any position along the inner walls of the pores of the carrier granule (in the form of a coating on the walls of the pores, wherein the coating may be discontinuous or continuous) to form a non- migrating physical barrier between coloring agent and the carrier.
  • the releasing agent For rapid color release into solution, it may be particularly advantageous to have the releasing agent "fixed” inside the pores but close the carrier granule surface so that a sustained rapid release of the coloring agent into wash water solutions months or years after the speckles are produced is achieved. This effect may not be achievable with liquid releasing agents, since they may continue to migrate into the core of the granule over time.
  • the amount of releasing agent present in the colored speckle may vary depending upon the nature of the porous carrier material or carrier and the desired performance of the resulting colored speckle. It may be desirable that the amount of releasing agent is enough to achieve sufficient release of the coloring agent into wash water. Greater amounts of releasing agent would not compromise the enhancement in the release rate, but too much releasing agent would compromise the bleed protection that the porous carrier provides. As a result, the optimum ratio of porous carrier to releasing agent may be the highest carrier to releasing agent ratio at which enhanced color release is enabled and which does not compromise bleed protection.
  • the weight ratio of carrier to releasing agent is in the range of 1000:1 to 1 :1, more preferably 500:1 to 1:1 , even more preferably from 50:1 to 1:1, and most preferably from 20:1 to 1.5:1. In other instances, it may be preferable that the weight ratio of carrier to releasing agent is 5 parts by weight of carrier to 2 parts by weight of releasing agent.
  • Optional additives that may be included in the colored speckles include perfumes, enzymes, bleach activators, bleaches, bleach catalysts, bleach stabilizers, foam regulators (foam boosters and antifoam agents), fluorescent whitening agents, soil repellents, corrosion inhibitors, soil antiredeposition agents, soil release agents, dye transfer inhibitors, builders, complexing agents, ion exchangers, buffering agents, and mixtures thereof.
  • Bleed inhibitors such as film forming polymers or polymeric coatings may also be included.
  • These additives may be included in addition to the coloring agent or as the sole active ingredient into the porous carrier that has been modified with the releasing agent.
  • One method for forming the colored speckles of the present invention includes the steps of providing a carrier, loading the carrier into a rotating drum or other suitable mechanical device, and providing heat to the drum.
  • the heat source may include any suitable source of heat that is capable of sufficiently elevating the temperature of the carrier.
  • a heat gun may be utilized.
  • the drum may or may not have baffles or other protrusions attached to its interior walls.
  • Heat may be applied to the rotating drum in order to elevate the temperature of the carrier to a temperature range of between 30°C and 90°C, more preferably between 40°C and 80°C. After the temperature of the carrier reaches its desired temperature range, a releasing agent may be added to the rotating drum.
  • the releasing agent may be added, preferably in the form of an aqueous solution (for instance, a salt solution), to the drum using any conventional means for adding materials to a container.
  • the releasing agent may be sprayed into the drum. The releasing agent thus comes into contact with the heated carrier.
  • the releasing agent may provide a substantially uniform coating on and/or into the carrier
  • the releasing agent may then be absorbed via capillary action into the pores of the heated carrier.
  • the releasing agent By evaporating of the water from the aqueous releasing agent solution, the releasing agent is deposited on the inner walls or surface of the pores of the porous granules. After completion of this step, the heat source may be removed.
  • the coloring agent preferably in the form of an aqueous solution, may be added to the carrier-releasing agent composite that remains in the rotating drum.
  • the coloring agent may be added to the drum using any conventional means for adding materials to a container.
  • the coloring agent may be sprayed into the drum.
  • the coloring agent thus comes into contact with the carrier-releasing agent composite.
  • the coloring agent may provide a substantially uniform coating on and/or into the carrier-releasing agent ;omposite.
  • the resulting colored speckle may have a final color-on-speckle loading of 0.01 % to 10%, more preferably of 0.1% to 5%.
  • the colored speckles may then be dried. Drying may be accomplished by any conventional means known for drying particulate materials.
  • the general methods for preparing the colored speckle described herein may not be construed as limiting the scope of the present invention. It should be possible, by way of alternative processing methods, to combine the carrier, releasing agent and coloring agent to produce a colored speckle which exhibits similar release profiles for the coloring agent, as well as other desired features, as the colored speckles produced by the general methods described herein and by their equivalent methods as known to those skilled in the art. For instance, it may be possible to combine the releasing agent and the coloring agent together into a mixture and then spray or otherwise apply the mixture to the carrier. It might also be possible to subsequently add additional coloring agent to the carrier. Also, it may be possible that a colored speckle having the desired characteristics may be manufactured by adding the carrier, the releasing agent, and the coloring agent together in one step.
  • Procedure 1 A coloring agent was sprayed directly on the carrier and no releasing agent was used. The procedure was performed according to the following steps:
  • the carrier was loaded into a rotating drum with baffles. The drum continued rotating for the entire procedure.
  • the coloring agent was sprayed onto the carrier in the rotating drum to form the colored speckles.
  • a releasing agent was applied to the carrier, followed by the addition of a coloring agent.
  • the procedure was performed according to the following steps:
  • the carrier was loaded into a rotating drum with baffles. Heat was applied from a heat gun angled at the side of the barrel. The temperature of the carrier was then monitored. The drum continued rotating for the entire procedure.
  • the carrier-releasing agent composite granules were then sprayed with a coloring agent that had been diluted with water to form the colored speckles.
  • the amount of water for the dilution was determined by the final target color loading desired on the speckle.
  • the carrier was loaded into a rotating drum with baffles. The drum continued rotating for the entire procedure.
  • the releasing agent-coloring agent solution was sprayed onto the carrier in the rotating drum.
  • Argel® 10 (a commercially available powder clay product), was used as the carrier. In order to granulate the powder into a particulate form, samples utilizing Argel® 10 were exposed to the following procedure prior to formation of the colored speckles:
  • test fabric piece (100% white cotton fabric) in a flat tray having dimensions of 36x24x6 cm.
  • test fabric piece (100% white cotton fabric) in a plastic tub having dimensions of 36x24x6 cm. The dimensions of the fabric piece are close to that of the tub.
  • Steps 1-5 were repeated to obtain a duplicate test sample. Results provided will be an average of the two test samples.
  • Test 1 Benefit of Modifying the Carrier with Releasing Agent
  • Test 4 Bleed Resistance of Colored Speckles
  • Test 5 Stain Testing of Colored Speckles
  • Test 6 Benefit of Modifying the Carrier with Releasing Agent: Applicability to
  • Test 7 Evaluation of Staining in Natural vs. Synthetic Clay Carrier Materials
  • Test 8 Evaluation of Staining in Natural vs. Synthetic (Partially and Fully
  • Test 9 Evaluation of Staining in Natural vs. Synthetic Clay Carrier Materials
  • Pelben® 10 pre-granulated sodium-bentonite 50
  • Pelben® 35 pre-granulated sodium-bentonite 50
  • the resulting colored speckles were added to Tide® powder laundry detergent.
  • One gram of the speckle-containing detergent was added to a clear plastic cup which contained 150mL of cold water. This mixture was gently stirred with a cotton swap for 30 seconds. The mixture was allowed to rest for 5 minutes, and then the mixture was stirred again with a cotton swap for 5 seconds. The color of the wash water in the plastic cup was then observed to see if it changed to blue and to determine if sediment was present in the bottom of the cup.
  • the speckles were also evaluated for various parameters such as quickness of the color release into the wash water. "Sediment” refers to the dispersed, water insoluble carrier that settles to the bottom of the cup under gravity.
  • This sediment may have varying degrees of color depending on how much of the color has released into the wash water solution.
  • the observation of no sediment being present is intended to describe that all visible traces of color have come off the speckles; it is not intended to describe the actual absence of solid uncolored sediment.
  • Amount of sediment at 1 minute was less than amount of sediment in Comp. Example 1A at 5 minutes.
  • Example 1C about equal to Example 1A; may be
  • Example 1 D about equal to Examples 1A and 1 C, or
  • Sediment amount at 5 minutes was less than amount at 1 minute.
  • the test results illustrate that the modification of the clay carrier with a releasing agent (e.g.
  • Liquitint® Blue HP polymeric colorant coloring agent 0.87
  • the resulting colored speckles were added to Tide® powder laundry detergent.
  • One gram of the speckle-containing detergent was added to a clear plastic cup which contained 150ml_ of cold water. This mixture was gently stirred with a cotton swap for 30 seconds. The mixture was allowed to rest for 5 minutes, and then the mixture was stirred again with a cotton swap for 5 seconds.
  • the color of the wash water in the plastic cup was then observed to see if it changed to blue and to determine if sediment was present in the bottom of the cup.
  • the speckles were also evaluated for various parameters such as quickness of the color release into the wash water.
  • “Sediment” refers to the dispersed, water insoluble carrier that settles to the bottom of the cup under gravity. This sediment may have varying degrees of color depending on how much of the color has released into the wash water solution. The observation of no sediment being present is intended to describe that all visible traces of color have come off the speckles; it is not intended to describe the actual absence of solid uncolored sediment.
  • the test results illustrate that the modification of the chalk (e.g. gypsum) carrier with a releasing agent (e.g. MgS0 4 salt) leads to a substantial decrease in the amount of time it takes to release the coloring agent from the colored speckle.
  • the releasing agent can therefore be used to make a quick color-releasing speckle with a porous chalk carrier.
  • test results provided herein illustrate that modification with a releasing agent leads to a decrease in the release time of the coloring agent from the colored speckle, regardless of the chemical nature of the porous carrier (e.g. clay or chalk).
  • the porous carrier e.g. clay or chalk
  • Granulated Argel® 10 (clay carrier) 50 Liquitint® Blue HP (polymeric colorant coloring agent) 0.25
  • Pelben® 10 (clay carrier) 25 Soda Ash (releasing agent) 3.9 Liquitint® Blue HP (polymeric colorant coloring agent) 0.85
  • Granulated Argel® 10 (clay carrier) 50 Sodium chloride (releasing agent) 17.5 Liquitint® Blue HP (polymeric colorant coloring agent) 1.75
  • Pelben® 10 (clay carrier) 50 Sucrose (releasing agent) 35 Liquitint® Blue HP (polymeric colorant coloring agent) 1.74 1 Samples made via Procedure 1.
  • the resulting colored speckles were added to Tide® powder laundry detergent.
  • One gram of the speckle-containing detergent was added to a clear plastic cup which contained 150ml_ of cold water. This mixture was gently stirred with a cotton swap for 30 seconds. The mixture was allowed to rest for 5 minutes, and then the mixture was stirred again with a cotton swap for 5 seconds.
  • Example 3C seconds of stirring. Most sediment remained. contained 2.8% of the speckles gone. Little Speckles completely colored speckle. sediment. Speckles disintegrated. After
  • Example 4A Bleed Resistance of Colored Speckles This test compares the bleed resistance of the colored speckles of the present invention.
  • the colored speckles of Example 1A which were made from a porous carrier modified with a releasing agent, were tested.
  • Example 4A was prepared as described below and was also tested for bleed resistance. In general, Example 4A was made by spraying the same color used in Example 1A onto a carbonate carrier and protecting, or coating, the coloring agent with bleed prevention coatings.
  • Soda Ash (granular carrier) 86.22
  • Liquitint® Blue HP polymeric colorant coloring agent 1.72
  • the Liquitint® Blue HP polymeric colorant was first sprayed onto the soda ash granules followed by the spray application of the corn oil and then the starch coating to the colorant-containing soda ash granules, according to methods described in Procedure 2.
  • Each sample tested for bleed resistance was prepared by adding 0.45 grams of the colored speckles to 30 grams of Breeze powder laundry detergent (a commercially available powder laundry detergent available from Unilever). The mixture was then placed in an unlined cardboard box in a controlled environment at 80% relative humidity and 37°C for a four week period of time. Each sample was then visually evaluated for the amount of color bleed that was observed to occur in the surrounding powder laundry detergent.
  • Breeze powder laundry detergent a commercially available powder laundry detergent available from Unilever
  • Example 1A and Example 4A were compared and visually evaluated for bleed resistance after four weeks in the Breeze powder laundry detergent.
  • Example 1A appeared to exhibit significantly greater bleed resistance than Example 4A. While Example 4A showed significant bleeding after 4 weeks, Example 1 A showed little to no bleed on the same detergent.
  • test results illustrate that the use of a porous carrier modified with a releasing agent provides a colored speckle that rapidly releases color into wash water, but also displays good bleed resistance in humid conditions.
  • TEST 5 Stain Testing of Colored Speckles This test illustrates the non-staining property of the colored speckles of the present invention.
  • Example 1 B as described herein, was independently added to the following powdered laundry detergents: Surf® (from Unilever), Tide® (from Procter & Gamble), OMO (from Unilever), Breeze (from Unilever), and Coral (from Unilever). Each sample was then tested according to
  • Two types of colored speckles were prepared by independently adding coloring agent or commercial dye to Pelben® 10 clay carrier.
  • "Type A” colored speckles were modified with 17 grams of magnesium sulfate releasing agent, as described previously in Procedure 2, prior to the addition of the coloring agent.
  • "Type B” colored speckles did not include any magnesium sulfate releasing agent, as described previously in Procedure 1 , prior to the addition of the coloring agent.
  • the following polymeric colorant coloring agents and commercial dyes were tested:
  • Example 6A Liquitint® Aztec Yellow lot 2009072027 (Phenyl based Azo) with
  • Comparative Example 6A Liquitint® Aztec Yellow lot 2009072027 (Phenyl based Azo) with no MgS0 4
  • Example 6B Liquitint® Orange X-96 (Bis-Azo) with MgS0 4
  • Comparative Example 6B Liquitint® Orange X-96 (Bis-Azo) with no MgS0 4
  • Example 6C Liquitint® Yellow LP lot E1279 (Methine Colorants) with MgS0 4
  • Example 6C Liquitint® Yellow LP lot E1279 (Methine Colorants) with no MgS0 4
  • Example 6D Liquitint® Red BL lot T1102 (H-Acid based Azo) with MgS0 4
  • Example 6D Liquitint® Red BL lot T1102 (H-Acid based Azo) with no MgS0 4
  • Example 6E Liquitint® Bright Blue/PC Cyan lot 2008242278 (Phthalocyanine) with MgS0 4
  • Example 6F Liquitint® Pink lot 2008469216 (Naphthol based Azo)
  • Comparative Example 6F Liquitint® Pink lot 2008469216 (Naphthol based Azo)
  • Example 6G Liquitint® Violet CT (AMTC based Azo) with MgS0 4
  • Example 6H Liquitint® Red ST lot A1091 (Benzothiazole Azo) with MgS0 4
  • Comparative Example 61 Liquitint® Patent Blue lot P1954 (TPM) with no MgS0 4
  • Example 6J FD&C Blue 1 lot HD138 (Water Soluble Commercial Dye)
  • Comparative Example 6J FD&C Blue 1 lot HD138 (Water Soluble Commercial Dye)
  • Example 6K Solvent Blue 35 lot 07020KZ (Water Insoluble Commercial Dye) with MgS0 4
  • Example 6L Acid Blue 80 (Water Soluble Commercial Dye) with MgS0 4
  • Example 6L Acid Blue 80 (Water Soluble Commercial Dye) with no MgS0 4
  • Example 6M Direct Violet 9 lot C1 141 (Azo Dye) with MgS0 4
  • the prepared colored speckles were added to Tide® powder laundry detergent such that the detergent contained 2% by weight of the colored speckles.
  • One gram of the speckle-containing detergent was added to a clear plastic cup which contained 150mL of cold water. This mixture was gently stirred with a cotton swap for 30 seconds.
  • the speckles were evaluated for quickness of the color release into the wash water. Test results are provided in Table 6.
  • Liquitint® Aztec Yellow polymeric colorant coloring agent
  • Pelben® 10 (clay carrier) 50 Magnesium Sulfate (releasing agent) 17 Liquitint® Orange X-96 (polymeric colorant coloring agent) 1.36
  • Pelben® 10 (clay carrier) 50 Liquitint® Orange X-96 (polymeric colorant coloring agent) 1.02
  • Pelben® 10 (clay carrier) 50 Liquitint® Yellow LP (polymeric colorant coloring agent) 1.02
  • Pelben® 10 (clay carrier) 50 Liquitint® Red BL (polymeric colorant coloring agent) 1.02
  • Liquitint® Red ST polymeric colorant coloring agent
  • Pelben® 10 (clay carrier) 50 Liquitint® Patent Blue (polymeric colorant coloring agent) 1.02
  • Solvent Blue 35 (commercial dye available from 1.36
  • Acid Blue 80 (a commercial dye available from 4.27 Aceto)
  • Acid Blue 80 (commercial dye) 3.2
  • test results illustrate that the colored speckles that were modified with a releasing agent exhibited an enhanced rate of color release for all classes of Liquitint® polymeric colorants, except for the AMTC-based Azo class represented by Liquitint® Violet CT. Additionally, the test results illustrate that the colored speckles that were modified with a releasing agent exhibited an enhanced rate of color release for the FD&C Blue, Patent Blue, Solvent Blue, and Direct Violet 9 commercial dyes. The test results illustrate that the release rate of Acid Blue 80 from the clay carrier does not appear to be enhanced by modification with magnesium sulfate releasing agent.
  • TEST 7 Evaluation of Staining in Natural vs. Synthetic Clay Carrier Materials The following samples were prepared generally according to Procedure 5, unless otherwise noted by the Process Description.
  • test results indicate that, for equivalent Violet DD color loading, colored (with Violet DD) natural sodium bentonite (Pelben® 35 or Argel® 40) powder provides less staining than colored (with Violet DD) synthetic sodium bentonite (Pelben® 10) powder. This result appears to be true regardless of the source of the natural sodium bentonite (e.g. Buntech or Fisher Scientific).
  • colored calcium bentonite (powdered and colored in lab) from AMCOL® provides equivalent staining as colored synthetic sodium bentonite (powdered and colored in lab) from AMCOL®.
  • Table 8 Partially Activated, Fully Activated, and Natural Bentonite Clay Powder Materials Colored with Liquitint® Violet DD Coloring Agent
  • the colored (with VDD) natural sodium bentonite powder provides less staining than the colored (with VDD) "activated” grades of bentonite powder (both partially and fully activated grades, which are synthetic sodium bentonites).
  • the colored (with VDD) fully activated bentonite powder provides less staining that the colored (with VDD) partially activated bentonite powder.
  • Sodium bentonite and calcium bentonite clay carrier material (granules/speckles) from AMCOL® were independently sifted. The clay carrier material that was retained by the #25 and #20 sieves for each of the sodium and calcium bentonite materials were separated.
  • Pelben® 10 and Pelben® 35 bentonite from Buntech were independently sifted and the clay carrier material that was retained by the #25 sieve for each of the bentonite materials was kept separate.
  • Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water (this is 3% color times 1.4 to compensate for color loss to the drum.)
  • Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water (this is 3% color times 1.4 to compensate for color loss to the drum.)
  • Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water (this is 3% color times 1.4 to compensate for color loss to the drum.)
  • Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water (this is 3% color times 1.4 to compensate for color loss to the drum.)
  • Liquitint® Violet DD (Lot PP012) was diluted to 5g with Dl water (this is 3% color times 1.4 to compensate for color loss to the drum.)
  • the colored speckles containing natural sodium bentonite provides less staining than the colored speckles containing synthetic sodium bentonite (Pelben® 10).
  • the colored speckles containing natural sodium bentonite provides less staining that the colored speckles containing calcium bentonite (from AMCOL®).
  • inventive colored speckles provide both quick release of non-staining color and bleed resistance to various detergent formulations with which they may be combined.
  • inventive colored speckles possess a significant advantage over currently available colored speckles by allowing rapid release of color into wash water, while still preserving bleed resistance and good non- staining properties.
  • the present colored speckles represent a useful advance over the prior art.

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Abstract

Cette invention porte sur des grains colorés sans dégorgement et à libération de couleur, destinés à être utilisés dans des détergents granulaires pour lessives et autres produits de consommation. Les grains se composent d'un support poreux, d'un agent de libération et d'un agent colorant.
PCT/US2010/002323 2009-08-25 2010-08-24 Grains colorés Ceased WO2011028249A1 (fr)

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EP10749928A EP2470631A1 (fr) 2009-08-25 2010-08-24 Grains colorés
CN2010800377084A CN102482618A (zh) 2009-08-25 2010-08-24 色粒
IN367DEN2012 IN2012DN00367A (fr) 2009-08-25 2010-08-24
JP2012526720A JP2013503237A (ja) 2009-08-25 2010-08-24 着色スペックル
ZA2012/00941A ZA201200941B (en) 2009-08-25 2012-02-08 Colored speckles

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US23670709P 2009-08-25 2009-08-25
US61/236,707 2009-08-25
US12/851,616 2010-08-06
US12/851,616 US8318652B2 (en) 2009-08-25 2010-08-06 Colored speckles comprising a porous carrier and a releasing agent layer

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US8476216B2 (en) * 2010-05-28 2013-07-02 Milliken & Company Colored speckles having delayed release properties
US10308900B2 (en) 2015-12-22 2019-06-04 Milliken & Company Occult particles for use in granular laundry care compositions
EP3318622B1 (fr) * 2016-11-04 2023-07-05 Sociedad Anónima Minera Catalano-Aragonesa Particules colorées pour détergents et leur procédé de production
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WO2013169828A1 (fr) * 2012-05-09 2013-11-14 The Procter & Gamble Company Composition de détergent de blanchisserie comprenant une particule contenant un colorant teintant et de l'argile
WO2013169536A1 (fr) * 2012-05-09 2013-11-14 Milliken & Company Composition de détergent de blanchisserie comprenant une particule comprenant un colorant teintant et de l'argile
CN104284969A (zh) * 2012-05-09 2015-01-14 宝洁公司 包含具有调色剂和粘土的颗粒的衣物洗涤剂组合物
JP2015524005A (ja) * 2012-05-09 2015-08-20 ザ プロクター アンド ギャンブルカンパニー 色相剤及び粘土を有する粒子を含む洗濯洗剤組成物
RU2600323C2 (ru) * 2012-05-09 2016-10-20 Дзе Проктер Энд Гэмбл Компани Моющий состав для стирки, содержащий частицу, включающую оттеночный агент и глину
US9540600B2 (en) 2012-05-09 2017-01-10 The Procter & Gamble Company Laundry detergent composition comprising a particle having hueing agent and clay
US9540599B2 (en) 2012-05-09 2017-01-10 Milliken & Company Laundry detergent composition comprising a particle having hueing agent and clay
CN104302752B (zh) * 2012-05-09 2018-03-09 美利肯公司 包含含调色剂和粘土的颗粒的衣物洗涤剂组合物
US10703912B2 (en) 2012-05-09 2020-07-07 Milliken & Company Laundry detergent composition comprising a particle having hueing agent and clay
US11066559B2 (en) 2012-05-09 2021-07-20 Milliken & Company Laundry detergent composition comprising a particle having hueing agent and clay

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ZA201200941B (en) 2012-10-31
IN2012DN00367A (fr) 2015-08-21
CN102482618A (zh) 2012-05-30
EP2470631A1 (fr) 2012-07-04
US20110053823A1 (en) 2011-03-03
JP2013503237A (ja) 2013-01-31
US8318652B2 (en) 2012-11-27

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